Countercurrent hydrotreating process



Feb. 8, 1966 D. D. MacLAREN 3,234,121

COUNTERCURRENT HYDROTREATING PROGES S Filed Jan. 2, 1962 Donald D. MocLuren lnvenror By M Patent Attorney United States Patent 3,234,121 COUNT ERCURRENT HYDROTREATING PROCESS Donald D. MacLarem'S'cotchPlains, N.J., assignor to Esso Research and .Epgipeering Company, a corporation of Delaware Filed Jan. 2,1962, Ser. No. 163,745

2 Claims. (Cl. 20 8-264) This invention pertains to the treatment of hydrocarbon oils with hydrogen in contact with a fixed bed of catalyst.

Catalytic 'hydrotreating processes involving the treatment of hydrocarbons, such ,as shale oil and petroleum oils, at elevated temperatures and in the presence of hydrogen in contact with a catalyst containing an active hydrogenating component have been practiced for some time. In some cases the .oil is only mildly treated to remove contaminants such as nitrogen and sulfur compounds, to reduce unsaturation and/or to improve color or stability. More severe :treatingmay be used to secure aromatics hydrogenation, molecular weight reduction, isomeriaation, cyclization, and the like. Such hydrotreating processes are known by a variety of names, such as hydrofining, hydrodesulfurization, hydrocracking, hydroisomerization, hydroforming and hydrocyclization.

In conventional systems, operating with an oil, an appreciable portion of which is non-vaporizable under the processing conditions, the fed stock is usually passed downwardly in mixed vapor-liquid phase over the catalyst in one or more reactors. Good contacting of both the vapor phase and the liquid phase with the catalyst is difficult to achieve. Liquid bypassing and consequent insufficient catalyst utilization is quite common. Liquid bypassing is particularly disadvantageous when one is attempting to obtain substantially complete elimination of a contaminant such as sulfur. These problems become greatly magnified when one seeks, for example, to scale up a hydrodesulfurization reactor from pilot scale to commercial'unit and obtain reactor efficiencies in the latter comparable with those obtained in the pilot unit. This is 'a particularly serious problem in a commercial unit because of the relatively large diameter of the reactor (5 to 12 feet) over which the liquid and vapor feed must be distributed as it passes through the catalyst bed. Based on, experience in packed distillation columns, one would expect that this would be a very poor system for obtaining intimate vapor liquid contacting and good liquid distribution. This has been found to be the case in actual experience. A light catalytic heating oil was subjected to hydrodesulfurization under the following conditions: 400 p.s. i.g., 600 F., 2 v./v./hr. and 900 s.c.f./b. of treat gas In the pilot unit the mass velocity Was 85 1bs./hI./sq. ft. while in the commercial unit the mass velocity was 1000 lbs./hr./sq. ft. The following table summarizes the results that were obtained in these runs.

Percentage of Sulfur Remaining Mid Boiling Point of Fraction Pilot Unit Commercial Unit aesawr 425r H was only about 10 percent. Equally important, however, is the efficiency as a function of boiling range. In the case of the pilot unit that portion of the feed in the vapor phase (i.e. midboiling range below about 510 F.) was desulfurized to 99-+%. However, as the transition occurred into the liquid phase region, the extent of desulfurization decreased as the boiling point of the fraction increased. This would be expected with good liquid distribution and vapor liquid contacting due to diffusional limitations in the liquid phase as compared to reaction rate limitations for the vapor phase. As may be seen from the above data, however, desulfurization of the vapor phase in the commercial unit is not particularly better than the liquid phase. This indicates that there is not only a liquid contacting problem but also a vapor liquid contacting problem. The vapor must be brought into equilibrium with the liquid so that the vapors can dissolve in the liquid, diffuse to the catalyst surface and react. Without this vapor-liquid transfer, reaction of the vapor phase is reduced.

Moreover, when one is attempting to obtain molecular weight reduction, e.g., cracking or hydrocracking of the oil, it is difiicult to keep the liquid oil phase in contact with the catalyst for the optimum time without overexposing and, in certain instances, underexposing the light vaporous products of the cracking. In other Words, satisfactory exposure to the catalyst of the vapor and liquid components of a mixed phase feed is almost impossible to attain with existing processes and equipment. In order to improve contacting it has been proposed to split the feed either within or exteriorally of the reactor and pass the liquid portion through one catalyst bed and the vapor portion through another catalyst bed in the same large vessel or in diiferent vessels.

The present invention is concerned with a process for improving feed-catalyst contacting in the hydrotreatment of oils, a substantial portion of which is liquid at the conditions of hydrotreating. It has been found that good contacting of both liquid and vapor can be obtained in a fixed bed hydrodesulfurization system by splitting the feed into two fractions which will be all liquid and all vapor under normal reaction conditions and feeding the liquid fraction to the top of the reactor and the vapor fraction and treat gas to the bottom of the reactor. Good liquid distribution and gas-liquid contacting is provided by a number of bubble cap trays or the like suitably spaced within the reactor. The liquid is periodically redistributed as it flows down through the reactor and the gas periodically re-contacts the liquid on the bubble cap trays as it flows up through the reactor. In this way good liquid distribution and good gas-liquid equilibrium is assured.

The present invention is particularly applicable to petroleum fractions boiling within the range of from about 200 F. to about 1000" F. such as kerosene fractions boiling in the range of about BOO-500 F., diesel fuels boiling in the range of about 300 to 650 F. and heating oil and gas oils having end boiling temperatures of up to about 1000 F. Usually the feed stocks treated advantageously in accordance with the present invention are of such a boiling range that about 1.0 to thereof will be vaporized under the temperature and pressure conditions obtaining in the hydrotreating reaction zone, and, hence, at least 10% remains liquid,

Suitable catalysts for the hydrotreating of hydrocarbon feed stocks in accordance with the present invention include molybdenum oxide or sulfide, nickel-tungsten sultide and, most frequently, cobalt molybdate or mixtures of cobalt oxide and molybdenum oxide supported upon an alumina-containing support or base, preferably activated or adsorptive alumina. In general, such catalysts are prepared. by first forming. adsorptive alumina particle's" in any suitable or known way and then compositing the.

active hydrogenation catalyst component thereonn Molybdenumoxide; can, for example, be added as a slurry or it may be applied as asolutionmfammonium mo- The cobalt oxide :can lbe=conveniently added lybdate.

as .a saltsuchas cobalt nitrate or acetate, salts which are readily decomposed to cobalt oxide and volatile materials.

The cobalt oxide. and the molybdenum oxide mayibe pro-- vided in equimolar amounts or a molecular excess. of

one over the other may be used; Suitable catalystscone tain fromabout 5 to about 25 wt. 'percent'of cobalt oxide and molybdenum oxide with the ratio of the former to the later inthe range of from about one to five to about five to one. The catalyst may, if desired, be given a pre-j treatment with hydrogen sulfide, carbondisulfide or the like in known manner in order to activate the same.

' The ,hydrofining reaction conditions vary somewhat de-. 1

pending upon the nature ofthe feed-stock, the'characterand quantity of the impurity or contaminant to be re:-;

moved and the degree of improvement desired. Reaction temperatures are generally within the range of from about 500 to about 800 F; and pressures mayrvary" from about 50 p. s.i.g. ,up' to. about 1500 .p.s.i.g., preferably about 200-400 p. s.i.g. Feed rates. to thehydrofining reactormay vary from about 0.25 to about ltl 'v.-/v./hr. Hydrogen orhydrogen-rich treat gasis supplied to the hydrofining reaction zone at the rate of from about to 3000 sci/b. with hydrogen consumption in the treatment ranging fromabout 1 to 1000 s.c.f./b. and

of from about 30 to 400 s. c.f./ b.

-In the.hydrofining of the foregoing hydroc'arbon frac. tions under the. conditions described thereis. a .gradual' deactivation of the catalyst. due :to -the accumulation alof carbonaceous or other deactivating deposits thereon.

When this occurs the catalystican be: regenerated-by disa continuing the supply of reactants, stripping hydrogen and hydrocarbon materials from the catalyst particles with steam andthen regenerating the catalyst by burning the carbonaceous deposits therefrom witha mixture ofair. anda diluentsuch as steam or. flue gas to limitithe tern-w perature reached in burning to the range-offrom about 'The present invention will be more readily understood with reference to the accompanying ;,drawing illustrating a diagrammatic flow planofthev process in accordance is normally in therange with this invention. In the drawing preheatedfresh feed and treat. gas are supplied through inlet line, l'lto-Y flash drum 2." The temperature and pressure conditions in flash drum are essentially the same; as inthehydrofining 're'-' action zo neso that there will separate therein the hydro-l tion from that portion ofdhe teed.whichremainsmnvaporized under the 'hydrofining :reaction conditions.

7 gen treat gas and the portion. of; the; hydrocarbon feed-i that will'be in vapor form .duringthe hydrofining opera- The unvaporiz'ed portion is withdrawn from the bottom a of flash drum Zfand charged via line 3 tothe upper portion of hydrofiningreactor vessel; 5. Thetreat gasand.

vaporized portionof the feed are taken overhead fromflash drurrr '2 and ehargedflvia line-lfl to the abOfllOmZf-Of reactor vessel 5.

The reactor vessel s is provided with an inlet tray'6 containinglinert fill to assist in the distribution :of the in.

coming liquid-to the vessel and spaced bubble cap trays or the like provide forgood liquid vgas contacting.

trays toadistribute the liquid leaving each, of the trays.v

streams were combined and cooled to condense out the Suitable restriction orifices are provided .in :the. several- Beds of catalyst 8, preferably a cobalt-oxide-molybdenum T oxide on activated. alumina, are provided above each of the bubble cap trays '7. Hydrofined liquid product is withdrawn from the lowermost tray 7 Lvia..line .9, and.

cooler 18 and passed to hydrofined product-storage. ,Tne-

treat gasand .the tvaporous feed fraction supplied to the bottom of the vessel 5 via' line 4 pass upwardly therethrough countercurrently to the downfiowing liquid. In.

' Composition; wt.''ipcrcent:

the process'in accordancewith the present-invention there is goodliquid-liquid distribution overzthe catalyst and,

most importantly, there is 'excellent vapor-liquid con-.-

tacting.

In the present arrangement'the vapor is, effec-.-

tively brought into equilibriumiwith tthefiliql idlFso that".

vapors can dissolve rill thelliquidgdifiuse tothe catalyst 7 surface and react: Without thisvapor-liquid,transfenre 1 action of the'vapor phase is reduced.

The vaporouskfractionsjof the feedand th'e1.accompanying gasesare-taken overhead fr-om reactor S'xthrough line a 11, cooled 'andcondensed ,inj'12 land dis'charged into gasliquid separator 13. The-.gaseoustproducts-are removed via'line 14 andidischarged'as fuel; or if .desiredg'subje cted to purification in knownmanner to; producea hydrogen containing gas aof-"sufficieht purity to recycle-Iintthe process. The de'sulfurized .orthydrofinedfiliquid product is I withdrawn from separator? 13.:{via i'line: lslftand 'passe'dto separate lightprodu'ct storage ;via,.line11t or 'pas'sed via-line 17 into, line 9for mixingvtwithdthe edesulfurized liquid product, therein and. thence to storage. 7

The following example; is'i iIIuStrativewf-the present invention; -v

ramble g A 430/610" F light catalytic cycle oiltwas'hydrofined' to remove sulfur ,and; nitrogen 'in'a'cgord ance Jv'yithf, .the

present invention.;;. The feed stoclgjhad-theffollowing in-.. spectionsz a Paraffins; 31.5 Condensed naphthenes-; Non-condensed g naphthenes Aromatics Distillationfi I IBP 544 57s FBP 6125 The feed andqIOOI s,c.f./fb. :of, hydrogenicontaining treat gas. were prehe'atedlto 650 F. at the hydrofining pressure lev el o f; about; 400; p. s.i. g'. Under thesei conditions ap-I proximat1Y,:39% 10f :thefeed ya OriZeds'J-The unf vaporized 'portion' of the-feed='.was'. fed to the'top-of the.

reactor while the :vap'orized portion plu'satrea't gas wasfed' to the bottom; Four. bubble ;cap plates :withv liquidlzre- 1 distributors werearranged equally spaced in the-reactor.

The catalyst: used was' {cobalt .molybdatez @on @alumina catalyst containingrapproximately "3.5 wt: .percent f CoO I and. 12.5 wt.'-.percent, M00 'I'he'lfeed -Was .charged to the; reactorat a space velocity1of"1'.0 lvivi/hrir' Treated liquid vwas withdrawn at thezreactor bottom and vaporized product and. treaty gas :from: the ireactortop. These treatedfeed. .The :liquicl product'was found to contain 3.5 p'.p'.m-. of nitrogenand 114 ppm. of sulfur, representing 9l and 9.7% removal respectively. f Approximately 400, s.c.f./b. of hydrogen were consumed, La. QII i case thle'same feed and hydr ofining conditions were used but under conventionabdownflow, mixi tlspliase; conditions.

In this caseless than a 0.5 v./v.'/hr.-was neededto give the m percent sulfur ns j ii r' gen'remdvauthusshowin the marked improvement effected by use of this invention. Theforegoing ;descriptioni contains; a limited .number:

under a toad thatinnrnerous va iations thereof:are still .withthe scope ofrthe present invention; Y a

What is claimed is:

1. The method of hydrotreating petroleum fractions boiling in the range of from about 200 F. to about 1000 F. at least 10% of which remains liquid during the hydrotreating which comprises heating the petroleum fraction and hydrogen-rich treat gas to reaction temperature, flashing the preheated feed at hydrotreating pressure into an all liquid and an all gaseous fraction, feeding the all liquid fraction to the top of a hydrotreating reaction zone for passage downwardly therethrough over a fixed bed of hydrogenating catalyst, feeding the all gaseous fraction directly to the bottom of said reaction zone for flow upward over said fixed bed of catalyst countercurrent to said downflowing liquid, periodically collecting the downflowing liquid as pools and discharging the pooled liquid at a large number of points over the cross section of the reaction zone to insure uniform distribution of the downflowing liquid, withdrawing hydrotreated liquid product from the bottom of said reaction zone and withdrawing hydrotreated gaseous fraction including excess treat gas from the top of said reaction zone.

2. The method of hydrotreating petroleum fractions boiling in the range of from about 200 F. to about 1000 F. at least 10% of which remains liquid during the hydrotreatnig which comprises heating the petroleum fraction and hydrogen-rich treat gas to reaction temperature, flashing the preheated feed at hydrotreating pressure into an all liquid and an all gaseous fraction, feeding the all liquid fraction to the top of a hydrotreating reaction zone for passage downwardly therethrough over a fixed bed of hydrogenating catalyst, feeding the all gaseous fraction directly to the bottom of said reaction zone for flow upward over said fixed bed of catalyst countercurrent to said downfiowing liquid, periodically collecting the downflowing liquid as pools, passing the ascending gaseous fraction through the pools of liquid to effect dissolution of the gaseous fraction in the liquid and discharging the pooled liquid at a large number of points over the cross section of the reaction zone to insure uniform distribution of the downflowing liquid, withdrawing hydrotreated liquid product from the bottom of said reaction zone and withdrawing hydrotreated gaseous fraction including excess treat gas from the top of said reaction zone.

References Cited by the Examiner UNITED STATES PATENTS 2,793,170 5/1957 Stiles et al. 208216 2,844,517 7/1958 Inwood 208210 2,877,099 3/ 1959 Bowles 208212 2,883,337 4/1959 Hartley et al 208254 2,893,942 7/1959 Berg 208-213 2,937,138 5/1960 Bevther 208-213 2,952,626 9/1960 Kelley et al. 208216 3,124,526 3/1964 Butler et a1. 208216 DELBERT E. GANTZ, Primary Examiner.

ALPHONSO D. SULLIVAN, Examiner. 

1. THE METHOD OF HYDROTREATING PETROLUEM FRACTIONS BOILING IN THE RANGE OF FROM ABOUT 200*F. TO ABOUT 1000* F. AT LEAST 10% OF WHICH REMAINS LIQUID DURING THE HYDROTREATING WHICH COMPRISES HEATING THE PETROLEUM FRACTION AND HYDROGEN-RICH TREAT GAS TO REACTION TEMPERATURE, FLASHING THE PREHEATED FEED AT HYDROTREATING PRESSURE INTO AN ALL LIQUID AND AN ALL GASEOUS FRACTION, FEEDING THE ALL LIQUID FRACTION TO THE TOP OF A HYDROTREATING REACTION ZONE FOR PASSAGE DOWNWARDLY THERETHROUGH OVER A FIXED BED OF HYDROGENATING CATALYST, FEEDING THE ALL GASEOUS FRACTION DIRECTLY TO THE BOTTOM OF SAID REACTION ZONE FOR FLOW UPWARD OVER SAID FIXED BED OF CATALYST COUNTERCURRNT TO SAID DOWNFLOWING LIQUID, PERIODCALLY COLLECTING THE DOWNFLOWING LIQUID AS POOLS AND DISCHARGING THE POOLED LIQUID AT A LARGE NUMBER OF JPJOINTS OVER THE CROSS SECTION OF THE REACTION ZONE TO INSURE UNIFORM DISTRIBTUION CALLING THE DOWNFLOWING LIQUID, WITHDRAWIONG HYDROETATED LIQUID PRODUCT FROM THE BOTTOM OF SAID REACTION ZONE AND WTIHDRAWING HYDROGREATED GASEOUS FRACTION INCLUDING EXESS TREAT GAS FROM THE TOP OF SAID REACTION ZONE. 